DE2306843A1 - CUMARIN COMPOUNDS HARDLY SOLUBLE IN WATER, THEIR PRODUCTION AND USE - Google Patents

Description

rcffeftfertwoffir i.-Fno, p. Throws "Dr. V. Si.r..i« ί- Kcwa

/ M ,, Gr, Esdicm «

SÄ R DO Z AG _Case

Basel / Schwexz

Camarin compounds that are sparingly soluble in water, their Manufacture and use

The invention relates to coumarin and coumarin-imide compounds free of carboxylic acid and sulfonic acid groups, to those in the 3-position an optional substituent carrying group of the formula

Kw N

⁰ 309835/1090

- 2 -. _ Case 15O-3374

w & zin K ^ signified hydrogen, an acyl group or an alkyl or phenyl group which may carry a special substance

is-

Mese VerMadüngen are excellent -as disperse dyes ^ for coloring. Fibers or threads made from fully or semi-synthetic , hydrophobic, high-molecular substances. Pie colorations obtained are characterized in particular by their Irichtechtheit _t brilliance "nd rtseist extremely strong fluorescence from grÜHstichige.

The new compounds correspond to the formula

309835 / 1.090

- 3 - Case 150-3374

where X is oxygen or = NH,

R is an optionally bearing substituent Alkyl or phenyl base,

R is hydrogen or one of the meanings of R , or R and R "together with the nitrogen atom attached to them a heterocyclic ring system,

R is hydrogen, an acyl or an optionally Alkyl, phenyl or heterocyclic radicals bearing substituents and

R. those for completing a carbocyclic or heterocyclic ring system aromatic character mean the necessary atomic groups

and the rings ι-, and R. v / can carry further substituents, but the molecule is free of carboxylic acid and Svtl füiiuäuregruppen.

309835/1090

- 4 - Case 150-3374

All alkyl groups on the molecule preferably contain 1, 2 ,. 3 or 4 carbon atoms and can, for example, contain one or more halogen atoms as substituents, including here generally in particular chlorine or bromine atoms are to be understood, alkoxy, hydroxy, cyano, rhodan, vinyl, amino, alkylamino, bialkylamino, phenylamino, N-phenyl-N-alkylamino, Wear phenyl, phenoxy, acyl, acyloxy or acylamino groups. Particularly preferred, for reasons of price, are unsubstituted methyl or ethyl groups.

All phenyl groups on the molecule and also those with A and R. denoted nuclei, can carry the above-mentioned substituents and, for example, also alkyl or nitro groups. A preferred one The meaning of R. is the radical of the formula -CH = CH-CH = CH-.

If R. and R_ together with the nitrogen atom bound to them mean a heterocyclic ring system, this generally means a 5- or 6-membered ring, optionally (as described above) bearing substituents, which, in addition to the = CH or - CH ₂ groups further heteroatoms,

309835/1090

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in particular oxygen atoms, sulfur atoms or nitrogen atoms may contain and may be saturated, unsaturated or aromatic in character.

Preferred acyl groups correspond to the formula R-Y- or R'-Z-, in which R denotes a hydrocarbon radical / the may carry the above-mentioned substituents and / or contain heteroatoms, preferably one optionally substituted alkyl or phenyl radical,

Υ a radical -OCO-, -SO - or -0-SO-, R ^{1 is} a hydrogen atom or R, Z is a radical -CO-, -NR ¹¹ CO- or -NR "SO -

and R "is a hydrogen atom or R.

t

The dyes of the formula are of particular interest

(I b)

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- 6 - Case 150-3374

where X is oxygen or = NH,

R _{11 is} an optionally hydroxyl, alkoxy, cyano,

Formyloxy, alkylcarbonyloxy, alkoxycarbonyloxy, alkoxycarbonyl or benzoyloxy as substituents carrying alkyl radical, an allyl or a phenyl radical,

R _{2 is} hydrogen or one of the meanings of R-. ·, »R-_ hydrogen, alkyl, _β phenyl, alkylaminoalkyl,

Alkylaminoalkylphenyl, thienyl, thiazolyl, > benzthiazolyl, methoxybenzthiazolyl, alkylcarbonyl, benzoyl, alkylsulfonyl, phenylsulfonyl or toluylsulfonyl,

B represent a methine group or a nitrogen atom,

the ring D by chlorine, bromine, methyl, methoxy, acetyl, Benzoyl, Methy! Sulfonyl, Phenylsulfonyl, Toluylsulfonyl,

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Case 150-3374

Antinosulfonyl or alkylaminosulfonyl substituted can be

and said alkyl and alkoxy radicals 1 to 4-carbon contain atoms. Alkylamino radicals are to be understood as meaning both mono- and dialkylamino groups.

The dyes of the formula are particularly preferred

(Ic)

3Q 983 5 / 1Q 9Q

- 8 - Case 150-3374

where X is oxygen or = NH and

R._ and R _n , independently of one another ethyl / cyanoethyl, "Xb

Acetoxyethyl, prapionyloxyethyl, methoxycarbonyloxyethyl, ethoxycarbonyloxyethyl, Methoxycarbonylethyl or ethoxycarbonylethyl mean »

The process for the preparation of the new compounds is characterized in that a compound of the formula

CO-NR ₃ -CO-N-

^R 6

^R 7

wherein R and R_ independently of one another hydrogen, a

Acyl or an optionally substituent-bearing alkyl or phenyl radical or Rg and R along with the one attached to them Nitrogen atom a hetero-. cyclic ring system, -

30 98 35/1090

- 9 - Case 150-3374

mean, with a dicarboxylic acid of the formula

HO -

T P

(LID,

HO-CO-

where R 'has one of the meanings of R_, or

condensed the anhydride of this dicarboxylic acid.

In the compound of the formula (II), R _ß and R _{7 are} preferably hydrogen.

The reaction of the compounds of the formula (II) with those of the formula (III) is generally carried out at temperatures between 160 ° and 240 ° C, being in a solvent or solvent mixture or without a solvent, in the melt, can be used. As a solvent aromatic solvents, e.g. tri-

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chlorobenzene, dichlorobenzene, nitrobenzene, pseudo-cumene,
Phthalic acid methyl, ethyl, propyl or butyl ester or durol can be considered. If the condensation is carried out in the melt, the reaction temperature is preferably between 200.degree. And 220.degree.

The compounds of the formula (II) are prepared, for example, by condensation of an aldehyde of the formula

(IV)

with a formula of the formula

CN

"C

ή ^ R ^(V)

R ₃ ^R 7

30 9 835/1090

- 11 - Case 150-3374

wherein the compound of the formula (II) is formed in which

X means a group = NH. This can be achieved by hydrolysis, splitting of the ring containing the imide group and renewed ring closure to the coumarin compound of Formula dl), in which X means oxygen> be transferred.

The condensation of the aldehyde of the formula (IV) with the ureid of the formula (V) is generally carried out in inert, preferably anhydrous solvents, for example ethanol, methanol, but preferably anhydrous dimethylformamide, dimethyl sulfoxide or dioxane, in the presence of an organic base, for example piperidine or pyridine, at temperatures between about 30 ⁰ C to 180 ° C, preferably at the boiling temperature of the corresponding! solvent under reflux. The reaction product of the formula (II) in which X denotes a group = NH usually falls during the course of the reaction

309835/109 0

■ ~ 1 ο -

Case 150-3374

as an insoluble product, otherwise it becomes e.g. by concentration and filtering off in a very pure state and in excellent condition Yield obtained.

The hydrolysis, splitting of the imide ring of the thus obtained Connection and the renewed ring formation takes place e.g. by boiling in organic acids (e.g. acetic acid) or diluted Mineral acids (1 to 10 percent hydrochloric acid) instead. It can be advantageous here to use the dilute mineral acid Add water-soluble, organic solvent, e.g. methanol or ethanol. The reactions mentioned and so that the formation of the compound of the formula (II) in which X is oxygen take place practically simultaneously.

309835/1090

13 - ' ' Case 150-3374

The processing of the new compounds of formula (la)

to coloring preparations is carried out in a generally known manner, e.g. by grinding in the presence of dispersing agents and / or Fillers. After adding more or less water, dye, pad or print in so-called long or short liquor. Pull the dyes from aqueous suspension excellent on textile material made from fully synthetic or semi-synthetic, hydrophobic, high molecular weight organic substances. They are particularly suitable for dyeing or printing textile material made of linear, aromatic polyesters, as well as cellulose-2 1/2 acetate, Cellulose triacetate and synthetic polyamides. One dyes or prints according to known ones, e.g. that in the French Patent No. 1,445,371.

The dyeings obtained have good all-round fastness properties ; to be emphasized are the lightfastness, the thermosetting , sublimation and pleating fastness »They are outstandingly wetfast, for example water- , » eerwaseer-, wash * - ujiä »sweat-fast, solvent-resistant, especially dry-cleaning-fast, peel-off medium ·! -, r <£ Ur ~ f about dyeing, oaon ^ # Eiwohgas-

309835/1090

ORIGINAL INSPECTED

Case 150-3374

and chlorine law; they are extremely resistant to pH differences in different dye baths, the effects of the various permanent pressing processes and the so-called "soil release" equipment. The resistance to reduction (when dyeing with wool) and the reserve of Wool and cotton are good.

In the following examples, the parts are parts by weight and the temperatures are given in degrees Celsius.

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example

15 parts of the compound of formula

CO - NH - CO - NH (a)

and 8 parts isatoic anhydride v / earth in a crucible, Triturated intimately under a nitrogen atmosphere and gradually heated to approx. 210 °. This forms under violent evolution of carbon dioxide and ammonia, a melt that for two hours under continuous Nitrogen flow is maintained between 200 ° and 220 °. After just one hour, however, the evolution of gas has practically come to a standstill. After cooling it will the reaction product is pulverized and can be used as a disperse dye after treatment that is customary in practice be, e.g. polyester fiber material with very

309835/1090

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good dyeing yield in yellow, strongly greenish fluorescent shades with excellent fastness properties will. ■ '

A chromatographically purified sample of the dye of the formula thus obtained

had a melting point of 262 °, elemental _analysis and mass spectrum give the empirical formula C 0n H ₁ -O ₀ N ₀ and

, ZL JLy J j

a molecular weight of 361 (/ = 361).

30 98 35/1090

- 17 - Case 150-3374

The U.V. spectrum of the substance dissolved in methanol gave:

= 214 mu (log £ = 4.65), = 291.5 rap (log £ = 4.09),

The ^ -urido ^ -N-diethylamino-cunia.rin {aJ can be as follows getting produced:

12.7 parts of the compound of the formula NC-CH ₀ CONHCONh ,,, prepared according to the information in German patent specification no. 175.415 and 19.5 parts of 2-hydroxy-4-N-diethylaminobenzaldehyde are dissolved in JOO parts of absolute ethajiol and, after 2 parts of piperidine have been added, they are briefly refluxed. The condensation product forms very quickly and precipitates in the form of yellow, needle-shaped crystals. It is filtered cold, washed with a little ethanol and dried.

28 parts of the compound thus obtained are dissolved in 400 parts of aqueous-alcoholic hydrochloric acid (200 parts 2 percent hydrochloric acid and 200 parts · ethanol) dissolved

309835/1090

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and refluxed for about an hour. The bright yellow, greenish fluorescent reaction product the formula

begins to precipitate during boiling and is filtered off after the reaction mixture has cooled down.

The dye of formula (b) can also be obtained in the following way:

30983571090

- 19 - Case 150-3374

Example la

7.5 parts of 3-Üreiäo-7-K-diethylamino-coumarin (formula (a) in first example) and 8 parts of isatoic anhydride Dissolved hot in 200 parts of trichlorobenzene with the addition of 0.1 part of boric acid and refluxed for three hours heated to boiling. The reaction mixture is then cooled, the precipitated product is filtered off, washed first with 100 parts of ethanol and then with 500 parts of petroleum ether and finally dried. The dye thus obtained is identical to the product obtained in Example 1 identical.

Example 2

15.1 parts of the compound of formula

NH

yJ- ^C
309835/1090

- 20 - Case 150-3374

and 6.5 parts of isatoesäureanhydrxd are in 250 parts of trichlorobenzene (Mixture of isomers) refluxed for 3 hours under a nitrogen atmosphere. Then, at boiling temperature, im In the course of 3 hours, a further 2.5 parts of isatoic anhydride are added and the reaction mixture under the same conditions treated for another 3 hours. After cooling, the insoluble product is filtered off, with a little trichlorobenzene and then washed with methanol and dried. The obtained dye of the formula

largely corresponds in its coloring properties those of the dye from Example 1.

- 309835/1090

- 21 - Case 150-3374

The ureido-7-N-diethylamino-2-imidocoumarin (d) can be like can be produced as follows:

12.7 parts of the compound of the formula NC-Ch ₂ CONHCONH ₂ , prepared according to the information in German patent specification no. 175,415 and 19.3 parts of 2-hydroxy-4-N-diethylaminobenzaldehyde are dissolved in 300 parts of absolute ethanol and, after the addition of 2 parts of piperidine, are briefly refluxed. The condensation product of the formula (c) forms very quickly and precipitates in the form of yellow, needle-shaped crystals. It is filtered cold, washed with a little ethanol and dried.

The following tables contain more examples of Color stiffeners of the formula (I a), these dyes are prepared analogously to the procedures of Example 1 and 2 manufactured; so each example corresponds to two dyes. All dyes dye hydrophobic fiber material in greenish yellow tones. In their properties are the coumarin and coumarin-imide compounds come in handy identical.

309835/1090

O ιη H

CH- - • O Zl ■ * cn m in 2306843 η - i OO • - in • r Ii O af ο O ta O {U * ta O jU> O CJ Ό U • a O Oil O O in Oil cn
ta I. CM O a O ta U a S3 O O O CM
O O CM 1 CJ CJ CJ CJ O O CJ O
I. I. Oil O O O O OI η JU ta Oil CM O
Q O approx pi - CJ JU ta Oil Oil CJ Oil in O CJ ta ta Oil JEf ta ta
O! Oil CM O O Oil 8th O U ü ta ta
CJ ta Oil Oil O O ta Yes ro I. O CJ O CJ ta I. O ο. B. ta
CJ O I. O I. υ CJ CM
K Oil I. »-. Oil CJ
O I. O ta S3 ία CM ta Oi ο CJ CJ 53 Oil Oil KO '. ". Oil U H U ta ta CM O I. CJ O O O ι I. I. O Oil I. ta - CJ O Oil ta ta 25th O CJ CJ O- I. Oil · <* OJ JU ta O O CM CM O ta ta CJ O I. I. - - - ■. Qt m ο in "· *-- «S3

309835/1090

Φ ω nJ U

te CO • CO • CO • CO Xl '· - ¹ p m • in in * in in • 2306843 Oil • • • υ te O te O te O te O te O te te O te te O O O O Il ο ο ■ Ο ο ο -a Oil • ö Oil Oil Oil Oil Ό CQ Ό te ο Oil Oil Oil O υ O α O a U υ ί £ te te • O O 1 1 O PJ CH- ο O ο ο O Oil Oil Ό Il Oil CM Oil ¹ O te M. te CO te te te te te in υ υ co in ο
ι te ιη ο U υ te Oil Oil te te do ο te I. ο Oil Oil te te O VO ο te ü α CJ Oil CO O co co co
PJ ο B. ο O t O rH Oil te te U ο Oil ι ro O CQ O O U Oil ο
ι te te 1 1 CQ I. 1 te ο υ γ » U Oil Oil ο rH I. • Η HO- γΗ U Oil ι CO ΐΗ ■ Η CO O CO ■ Η te in Ό te CO Γ) te ο W. Oil ο O te υ ο Oil CO ο ο I. ο te ο Oil O ο ο te Oil co Oil I. O ο • • PJ te te Oil Oil O O O ο ο te te Ό Oil * - * ι ο ο VO te Oil 1 rH ο Oil O K I. O ¹ O Oil O O te tJ rH υ PJ Oil U I. in σι ■ Η i-t rH Oil Tue ω ο

309835/1090

(U to ti U

te ü

Il O

Il

cn

CM

οι

cn -'-.

ίο υ

O Ϊ3 ι CM W. O CM ίο υ

CM

ta κ

ta

O CM O 1

ιη

ίο

CM

OJ

ro (N

CN

CSJ

CM

CO CM

309835/1090

O) co id O

JU • ιη • • • ZS • O O O O O O Il Ό CM «Ö pi O υ ι ο Il ιη ο do do to νο • ro do O O ο; I. ¹ U * • in O ο CM te {Tj VO O ιη SJ CO νο ω O O CM O PO O ta O tn O ο O O Il α O CM CM CM (X * υ K O do ι O O O CM CM CM CM ω do te ta ο O O U ι I. I. ¹ CM CO "S ¹ ro co ro CO ä · σι (Q O CM (Q 55

309835/1090

Case -ISO-

The following Table 2 contains the dyes

formula

R;

N -

Oil

fQ

11
in Oil in 6th • • O • ό • O * ό • 2306843 ο • O f O in d • O ία ία Ό O O O Ό O ο Ό O O Ό O ■ a ta O 1 Oil • Ö • υ ■ ϋ «Ö • ϋ Oil 'Ö Oil O Oil O O ^, ιη CQ ro ro SJ I. ίο ra VO in in U O υ ιη ro ro Oil ro ro ία approx ία Eu K VD J2J - VO υ O U O Oil Oil Oil υ OJ O O CJ U i-l O in O O • O • ο ta O ιη O Oil m U O • - * xj CQ CQ ο CQ O CJ ο I. ία ία ία ία O Oil I. I. I. • Ö 1 Oil Oil 53 . U O ία ο I. Oil I. 1 ο ία ro ι ο ία ι ο in CO σ \ ο τ-Λ ο ro ro ro ro ο in Oil ο ία pi Oil Oil > α U ο I. Oil Ü I. i-l pi 10 O mis

309835/1090

ro η I

in Il ro in I. m • Il • 2 8 m 03 do O O O O fN CN I. Ό I. I. O I. ro CN - W pi O in O I. i-T • in : 03 • O Ά O CN m U
I. • O ! S O U • d CN ΪΒ O fi ·
CQO CN ma S3 O r ~ I. VO OO ■ <*

3098 35/1 OaO

- 29 - Case 150-3374

APPLICATION EXAMPLE

7 parts of the dye prepared according to Example 1 v / earth with 4 parts of sodium dinaphthylmethanedisulphonic acid, 4 Parts sodium cety! Sulfate and 5 parts anhydrous Ground sodium sulfate to a fine powder in a ball mill for 48 hours.

1 part of the dye preparation obtained in this way is made into a paste with a little water and the suspension obtained through a Sieve added to a dyebath containing 3 parts of sodium lauryl sulfate in 4000 parts of water. The liquor ratio is 1:40. 100 parts of purified polyester fiber material are then added to the bath at 40-50 °, and 20 parts are added Parts of a chlorinated benzene are emulsified in water, the bath is slowly heated to 100 ° and stains for 1-2 hours at 95-100 °. The bright green-tinged yellow colored fibers are washed, soaped, washed again and dried. The level coloring is excellent light, overdyeing, washing, water, sea water, sweat, subliming, flue gas ,, thermofixing, pleating and permanent press-proof.

30983 5/1090

Claims (1)

Case 150-3374 Claims cn e 1. Coumarin compounds of the formula which are sparingly soluble in water (Ia) 309835/1090 - 31 - Case 150-3374 where X is oxygen or = ΝΗ, R is an optionally bearing substituent Alkyl or phenyl radical,
R is hydrogen or one of the meanings of R 4 * JL or R ₁ and R_ together with the nitrogen atom attached to them form a heterocyclic ring system, R is hydrogen, an acyl or an optionally Alkyl, phenyl or heterocyclic radicals bearing substituents and R. those for completing a carbocyclic or heterocyclic ring systems of aromatic character necessary Mean atomic groups and the rings A and R can carry further substituents, but the molecule of carboxylic acid and Sulfonic acid groups is free. 30 9835/1090 Case 150-3374 2. Coumarin compounds which are sparingly soluble in water according to Claim 1, the formula 12th (I b) where X Oxygen or = NH, an optionally hydroxyl, alkoxy, cyi-.i, formyloxy, alkylcarbonyloxy, alkoxycarbonyloxy ', 30 98 35/1090 _ 3 3 - Case 150-3374 Alkoxycarbonyl or benzoyloxy as a substituent-bearing alkyl radical, an allyl or a phenyl radical, R_ hydrogen or one of the meanings of R, -, /. R _{3 is} hydrogen, alkyl, phenyl, alkylaminoalkyl, alkylaminoalkylphenyl, thienyl, thiazolyl, benzthiazolyl, methoxybenzthiazolyl, alkylcarbonyl, benzoyl, alkylsulfonyl, phenylsulfonyl or toluylsulfonyl, B represent a methenyl group or a nitrogen atom, the ring D by chlorine, bromine, methyl, methoxy, acetyl, Benzoyl, methylsulfonyl, phenylsulfonyl, toluylsulfonyl, Aminosulfonyl or alkylaminosulfonyl may be substituted and said alkyl and alkoxy radicals 1 to "4 carbon contain atoms. 309835/1090 Case 150-3374 3. Coumarin, which is sparingly soluble in water, can be used in compounds Claim 1, the formula. · (I c) where X is oxygen or = NH, R and R independently represent ethyl, cyanoethyl, Äcetoxyätiiyl , Propionyloxyäthyl, Methoxycarbonyloxyäthyl, Aethoxycarbonyloxyäthyl, Methoxycarbonyläthy1 or Aethoxycarbony1-ethyl. 4. The compounds of the formula (I a) according to
Claim 1, V7orin X is oxygen. 309835/10 9 0 Case 150-3374 5. Process for the preparation of compounds of the formula which are sparingly soluble in water (Ia) where X Oxygen or "KH _t an optionally substituted alkyl or phenyl radical, 309835/10 9 0 - 36 - Case 150-3374 R is hydrogen or one of the meanings of R or R and R_ together with the nitrogen atom bonded to them form a heterocyclic one Ring system, R is hydrogen, an acyl or an optionally Alkyl, phenyl or heterocyclic radicals bearing substituents and R. those for completing a carbocyclic or heterocyclic ring systems of aromatic character mean necessary atomic groups and the rings A and R. can carry further substituents, but the molecule of carboxylic acid and
Sulphonic acid groups is free <, characterized in that one is a compound of the formula 309835/1090 - 37 -, Case 150-3374 wherein R ,. and R "independently of one another hydrogen or an optionally substituted alkyl or phenyl radical or R, and R " together with the nitrogen atom attached to them a heterocyclic ring system mean, with a dicarboxylic acid of the formula HO - CO ^^ - ^ , Ju- HO-CO-N- H wherein R ^ has one of the meanings of R ₃ , or condensed the anhydride of this dicarboxylic acid. 309835/10 90 - 3 ⁸ - Case 150-3374 G. Use of the dyes of the formula (I a) according to Claim 1 for dyeing or printing fibers or Threads or materials made from them made of fully or semi-synthetic, hydrophobic, high molecular weight organic substances. 7. Process for dyeing or printing fibers or
Threads or materials made from them made from fully or semi-synthetic, hydrophobic, high molecular weight organic substances with dyes of the formula (Ia) according to claim. 1. 8. The dyed or printed according to claim 6
Materials. 3700 / HW / HSc 309835/1090